Method for manufacturing a hardened lead storage battery electrode

ABSTRACT

A method for manufacturing a hardened lead storage battery electrode wherein fine, particulate solids, that are insoluble in lead, are incorporated into a lead matrix. The method includes the steps of incorporating solids, dissolved or suspended in an electrolyte, into a lead matrix such that shaping simultaneously occurs during the deposition of lead due to a suitable fashioning of a plurality of electrically conductive surface regions; vigorously agitating the electrolyte by introducing air through an apertured plate in the bottom of an electrolyte vessel providing an electro-chemical cell including a cathode and a Cu/Ta/Pt anode and an electrolyte solution including HBF 4  and an electrolyte selected from PbO, Pb(OH) 2  and PbCO 3  or including a graphite anode and an electrolyte solution of Fe(BF 4 ) 2  and Fe(BF 4 ) 3 . The electrolyte is prepared from a raw material selected from lead, waste material containing lead and desulfured lead storage battery electrolyte paste. The deposition is carried out at a current density of about 100 to about 2000 A/m 2 .

This application is a 371 of PCT/DE 95/00112 filed Jan. 27, 1995.

This application is a 371 of PCT/DE 95/00112 filed Jan. 27, 1995.

BACKGROUND OF THE INVENTION

The invention is directed to a method for manufacturing a hardened leadstorage battery electrode, finely particulate solids that are insolublein lead being dispersively distributed in the lead matrix thereof.

Plate grids for lead accumulators are mainly manufactured by gravitycasting into moulds by hand or with casting machines and by diecastingwith warm chamber or cold chamber diecasting machines. Continuousgravity casting with a drum casting machine and subsequent gridfabrication according to the expanded metal technique is alsosignificant. Punching and stamping of plate grids and build-up weldingof pre-fabricated grid parts, for example extruded rods on the basis ofgravity casting or diecasting, are less wide-spread. The manufacturingmethods respectively comprise specific disadvantages. In gravitycasting, the minimum plate thickness is limited to 1 mm and the platethickness is not constant due, among other things, to irregular erosionof the coating in the casting mold. The diecasting method requires aspecific viscosity of the molten metal. For example, lead-antimonyalloys having an antimony content of 3 through 8% are therefore notcapable of being processed. In continuous gravity casting in a drumcasting machine, the minimum plate thickness is limited to approximately1 mm. The utilization of the raw material is comparatively low in gridmanufacture by punching and stamping and the possibilities of griddesign are limited. The manufacture of a grid according to the expandedmetal technique does not allow a complete optimization of the gridgeometry.

Lead alloys are employed as materials for the lead storage batteryelectrodes since the apparent yield stress (static strength) and thecreep resistance (long-time rupture strength) of pure lead are too low.

In order to increase the strength of lead, it is alloyed with elementssuch as, for example, antimony or calcium and tin, whereby solidsolution hardening and dispersion hardening take effect (W. Hofmann,Blei und Bleilegierungen, Springer-Verlag, Berlin/Gottingen/Heidelberg1962). These alloy elements, however, fundamentally raise the electricalresistance and often have a disadvantageous influence on theelectrochemical properties such as the corrosion behavior and thebattery behavior due to the formation of gas.

In the light of this background, methods were developed in order toincrease the strength of lead storage battery electrodes by dispersionhardening, whereby particles that are insoluble in lead and have apredetermined size and optimally small average spacing must bedispersively integrated into the lead material. Various methods ofpowder metallurgy have been proposed for producing a lead oxidedispersion in lead in U.S. Pat. No. 3,253,912 and by A. Lloyd, E. R.Newson, "Dispersion strengthened lead: developments and applications inthe chemical industry", Proc.Conf.on Lead, 1968, 255-267. A powdermetallurgical method for producing an aluminum oxide dispersion in leadwas disclosed by M. M. Tilman, R. L. Crosby, D. H. Desy, Dispersionstrengthening of lead by coprecipitation, Report BM RI 7570, U.S.Department of the Interior, Washington 1971. These methods, however, allhave the disadvantage of non-optimum particle size and dispersion and ofcomparatively high cost, and also lead to technical problems such asunfavorable electrochemical behavior and lack of weldability. Economicaland technical difficulties are thus established in these methods fortechnical application, for example in batteries.

Fundamentally, thin metal layers with dispersively distributed phasesembedded therein can be manufactured by precipitation onto solid bodiesfrom all metals with which an electrodeposition is possible such as, forexample, copper, nickel, iron, zinc and lead.

According to the current state of the art, particles of graphite, PTFE,Al₂ O₃, SiC and other substances are introduced into galvanic layers(dispersion coatings) in that they are deposited on the substratesimultaneously with the metal, being deposited from a suspension in theelectrolyte under controlled conditions. This state of the art led tonumerous works about methods for improving the properties ofelectrodeposited dispersion coatings. The dispersion coatings areemployed as functional surface coatings, particularly as anti-wearcoatings with nickel as metal matrix. A high proportion of thedispersively integrated phase (dispersoid) given optimally uniformdistribution of the dispersoid in the metal matrix is desired in manyinstances. Thus, DE-AS 22 36 443 discloses an amino organosiliconcompound, DE-AS 26 43 758 discloses a cationic as well as a non-ionicfluorocarbon compound, DE-AS 26 46 881 discloses imidasoline hydroxides,and DE-AS 26 46 881 discloses dimethylaminoxides as additives forincreasing the deposition rate of the dispersively integratedconstituent.

Wiener et al. (Plating 4, 1970, pages358 through 361) disclosed thehardening of electrolytically deposited lead and lead alloys byemploying specific additives and embedding dispersoids. Of the additivesinvestigated, the combination of lignin sulfonic acid and cumarin provedmost effective. They achieved the desired increase in hardness only byadding TiO₂ with an average grain size of 0.03 through 0.01 μm. Thecurrent density amounted to 270 through 540 A/m².

Japanese published application JP-O-47 11264 discloses a method for theelectrolytic manufacture of coatings and galvanoplastics from leadmaterials upon employment of an electrolyte that containsPb-fluoroboride, Pb-fluorosilicate or Pb-sulfamate, 0.0005 through 5 g/lcopper and, optionally, 0.025 through5 g/l of a high-molecularpolyacrylamide. The solution is agitated with a magnetic agitator. Thelead deposition is implemented with lead plates as anode, steel platesas cathode and with a current density of 500 through 1000 A/m².

According to current opinion, lead materials that contain metals withlow hydrogen overvoltage promote self-discharge due to hydrogendevelopment at the negative electrode. Lead itself has an extremely highhydrogen overvoltage. When the lead electrode is therefore combined inan electrolyte solution with another metal having a low hydrogenovervoltage, then a correspondingly more pronounced development ofhydrogen occurs at this electrode and the lead electrode is dischargedcorrespondingly faster. This is also true of metals that areelectrodeposited on the electrode (formation of local elements).Particularly the metals having extremely low hydrogen overvoltage(precious metals, silver, nickel, copper) can increase the developmentof hydrogen to such an extent that a pronounced formation of bubblesbegins, the term "continued gassing metals" deriving therefrom (manual"Bleiakkumulatoren", Varta Batterie AG (editor), VDI-Verlag, Dusseldorf1986). The employment of a copper-containing lead storage batterymaterial for the positive electrode therefore does not seem meaningful.

SUMMARY OF THE INVENTION

A goal of the invention is a method for manufacturing a hardened leadstorage battery electrode having properties improved compared to purelead and lead alloys hitherto employed that can be economicallymanufactured in technically usable, short times.

This is inventively achieved in that the solids dissolved or suspendedin the electrolyte during an electrolytic lead deposition areincorporated into the lead matrix; in that the shaping ensues at thesame time during the deposition due to a suitable fashioning of theelectrically conductive surface regions; in that the electrolyte ishighly agitated by introducing air through an apertured plate in thebottom of the electrolyte vessel; in that the current density amounts to100 through 2000 A/m², preferably 600 through 2000 A/m² ; in that theelectrochemical cell is composed of a cathode as well as of a Cu/Ta/Ptanode; and in that HBF₄ solution as well as lead, waste materialcontaining lead and/or desulfured lead storage battery electrolyte pasteare employed as raw materials for the production of an electrolyte thatcontains PbO, Pb(OH)₂ or PbCO₃.

What is to be understood by "suitable fashioning of the electricallyconductive surface regions of the cathode" is that the electricallyconductive surface regions of the cathode form a specific pattern thatcorresponds to the desired shape of the deposited battery electrode.

Compared to traditional electrodes for lead storage batteries, thedispersion hardened lead storage battery electrodes manufacturedaccording to the inventive method have improved mechanical propertiesand a reduced electrical resistance. The static strength and the creepstrength are increased, this enabling a reduction of the supportingcrossection of the electrodes. This reduction in crossection allows anincrease in the weight-related energy storage density without negativelyinfluencing the electrochemical properties of the battery electrode. Bycontrast to traditional battery electrodes, no limits are thereby placedon a reduction in crossection due to the manufacturing method. Theinventive method thus guarantees a rapid and uniform deposition of thelead material. The cost-beneficial manufacture of a lead storage batteryelectrode is thus possible. A complicated and expensive finishingoperation is not required, namely, due to the net shape and technicallyusable structure and Surface quality of the deposited battery electrode.Moreover, thickness and shaping of the battery electrode can be variedwithin broad limits, the possibility of maximum paste utilization due tothe optimization of the thickness and the contact area with theelectrode deriving as a result. Further, the inventive method yields thepossibility of varying the proportion of solids built into the leadmatrix for a given composition of the electrolyte by setting a specificcurrent density. It has been shown, namely, that, for example, therelative copper part built into the lead matrix with reference to thecopper content of the electrolyte solution increases with lower currentdensity.

The object underlying the invention is also achieved by a method whereinthe solids dissolved or suspended in the electrolyte are integrated intothe lead matrix during an electrolytic lead deposition, wherein theshaping ensues at the same time during the deposition due to a suitablefashioning of the electrically conductive surface regions of thecathode, wherein the electrolyte is highly agitated by introducing airthrough an apertured plate in the floor of the electrolyte vessel,wherein the current density amounts to 100 through 2000 A/m², preferably600 through 2000 A/m², wherein the electrochemical cell is composed of acathode, a diaphragm as well as a graphite anode, and wherein a Fe(BF₄)₂/Fe(BF₄)₃ solution as well as lead, waste material containing leadand/or lead scrap are employed as raw materials for the production ofthe electrolyte.

With this modification of the inventive method, specific waste materialssuch as, for example, used lead storage battery electrodes or electrodepaste can be employed as raw materials for the production of theelectrolyte, this denoting a further cost-saving for the manufacture ofdeposited lead storage battery electrodes.

It is provided in a further development of the invention that 50 through300 g/l Pb⁺⁺, 50 through 200 g/l free HBF₄ and 1 through 5 g/l H₃ PO₄are contained in the electrolyte. The formation of PbO₂ isadvantageously prevented with the addition of H₃ PO₄.

It is provided in a further development of the invention that 50 through200g/l Pb⁺⁺, 10 through50 g/l Fe⁺⁺, 0.1 through 5 g/l Fe⁺⁺⁺ and 10through 100 g/l free HBF₄ are contained in the electrolyte.

It is provided in a further development of the invention that thecurrent density amounts to 1100 through 2000 A/m². These extremely highcurrent densities assure very high deposition rates and, thus, veryshort manufacturing times of the battery electrode.

It is provided in a further development of the invention that, due to asuitable shaping of the cathode or an insulating covering of the cathodein a specific pattern, the deposited material at the electricallyconductive surface regions of the cathode yields the shape of a grid.

It is provided in a further development of the invention that gelatines,glue, β-naphthol, rescorcin, calcium lignin sulfonate and/or peptone isadded to the electrolyte as additive in a concentration of 0.1 through 2g/l each. The addition of these additives assures an especially uniformdeposition of the lead and of the solid.

It is provided in a further development of the invention that apolyacrylic acid amide as added to the electrolyte as additionaladditive in a concentration of 0.05 through 5 g/l . The addition of thisadditive promotes the uniform deposition of the lead and of the solid.

It is provided in a further development of the invention that thecompound Y₂ O₃, Al₂ O₃, ZrO₂, SiO₂, TiO₂, SiC, WC, TiC, BaSO₄, BN and/orSi₃ N₄ in a concentration in the electrolyte of 5 through 150 g/l eachand/or the metal Sn, As, Sb, Bi, Cu, Se, Te and/or Ag in a concentrationin the electrolyte of 0.01 through 5 g/l each is employed as solid.

It is provided in a further development of the invention that the metalSn, As, Sb, Bi, Cu, Se, Te and/or Ag is employed in a concentration inthe electrolyte of 0.01 through 5 g/l each.

It is provided in a further development of the invention that thecompound Y₂ O₃, Al₂ O₃, ZrO₂, SiO₂, TiO₂, SiC, WC, TiC, BaSO₄, BN and/orSi₃ N₄ is present in a grain size of 0.005 through 5 μm.

It is provided in a further development of the invention that theelectrolytic lead deposition is implemented at temperatures between 30 °and 90° C.

It is provided in a further development of the invention that thecathode is composed of a plate of an electrical insulator material withelectrically conductive tracks applied thereon, the lead materialdepositing on said tracks and their arrangement thus defining theshaping.

It is provided in a further development of the invention that a coppertrack is employed as electrically conductive track, this beingmanufactured by leeching a copper layer that is applied on theelectrical insulator material and is covered with a mask, whereby themanufacture of the mask ensues in a phototechnical way.

It is provided in a further development of the invention that theelectrolytically deposited, hardened lead electrode is after-coated withpure lead. The corrosion resistance of the lead electrode is improved bythe after-coating with pure lead, for example high-purity lead.

The subject matter of the invention shall be set forth in greater dealbelow with reference to examples.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A lead storage battery electrode, pursuant to the present invention, maybe manufactured according to the following examples.

EXAMPLE 1

PbO that is dissolved in HBF₄ in a drum mixer is utilized as rawmaterial for manufacturing the electrolytic solution. Pb(BF₄)₂ arises:

2 HBF₄ +PbO-→Pb(BF₄)₂ +H₂ O.

The lead is deposited at a cathode in an electrolysis cell from theaqueous Pb(BF₄)₂ solution, which contains 150 g/l Pb⁺⁺, 100 g/l freeHBF₄, 2.5 g/l H₃ PO₄, 0.6 g/l glue as well as 0.4 g/l calcium ligninsulfonate, this cathode being composed of an epoxy resin carrier andcopper tracks applied thereon in the form of a grid. Oxygen is releasedat an anode that is composed of a copper/tantalum/platinum wire:

Pb(BF₄)₂ +H₂ O-→Pb+2 HBF₄ +1/2 O₂.

The solid suspended in the electrolyte, SiC powder having an averagegrain size of 1 μm and in a concentration of 50 g/l or copper in aconcentration of 0.4 g/l, is held in suspension and circulated about 10times per hour by introducing air through an apertured plate in thefloor of the electrolyte vessel. The electrolytic lead deposition isimplemented at a temperature from 35 through 45° C. and given a currentdensity of 800 and 1200 A/m². Dispersion hardened lead storage batteryelectrodes having a thickness of 0.3 through 0.6 mm are manufacturedwith this method. The dispersoid contents in the lead matrix amount toup to 4 mass percent SiC or up to 0.8 mass percent copper. Theincorporation of the dispersoids into the lead storage battery electroderesults in a clear increase in strength compared to an electrode of purelead. Whereas the electrode of pure lead has a hardness value #3(19/62,5/30) of 4, the dispersion hardened lead storage batteryelectrodes achieve hardness values of 8 through 10 (SiC dispersoids) and20 through 24 (copper dispersoids).

EXAMPLE 2

Lead scrap in the form of used lead storage battery electrodes that aredissolved in Fe(BF₄)₃ are utilized as raw material for manufacturing theelectrolyte solution. Pb(BF₄)₂ arises:

2 Fe(BF₄)₃ +Pb-→Pb(BF₄)₂ +2 Fe(BF₄)₂.

The lead is deposited at a cathode in the electrolysis cell from theaqueous Pb(BF₄)₂ solution that contains 30 g/l Fe⁺⁺, 1 g/l Fe⁺⁺⁺, 30 g/lfree HBF₄ as well as 1 g/l glue:

Pb(BF₄)₂ -→Pb+2 BF₄ ⁻.

The cathode is composed of an epoxy resin carrier and copper tracksapplied thereon in the form of a grid. Iron is oxidized at a graphiteanode that is separated from the cathode by a diaphragm:

Fe(BF₄)₂ +BF₄ ⁻ -→Fe(BF₄)₃.

The solid suspended in the electrolyte, SiC powder having an averageparticle size of 1 μm and in a concentration of 50 g/l therefor copperin a concentration of 0.4 g/l, is kept in suspension and circulatedabout 10 times an hour by introducing air through an apertured plate inthe bottom of the electrolyte vessel. The electrolytic lead depositionis implemented at a temperature of 35 through 45° C. and given a currentdensity of 800 and 1200 A/m². Dispersion hardened lead storage batteryelectrodes having a thickness of 0.3 through 0.6 mm are manufactured.The dispersoid contents in the lead matrix amount to up to 4 masspercent SiC or 0.8 mass percent copper. The incorporation of thedispersoids into the lead storage battery electrode results in a clearincrease in strength compared to an electrode of pure lead. The hardnessvalue of the electrode of pure lead HB(19/62,5/30) amounts to 4. Bycomparison thereto, the dispersion hardened lead storage batteryelectrodes comprise hardness values HV of 8 through 10 (SiC dispersoids)and 20 through 24 (copper dispersoids). Electrochemical measurementsshow that the hydrogen over-voltage at the electrodes dispersionhardened with Cu is not significantly lowered within the framework ofthe obtainable accuracy of measurement, namely both compared to lead aswell as to commercially obtainable lead storage battery electrodematerials.

The invention is not limited to the particular details of the methodsdescribed and other modifications and applications are contemplated.Certain other changes may be made in the above-described agent withoutdeparting from the true spirit and scope of the invention hereininvolved. It is intended, therefore, that the subject matter in theabove description shall be interpreted as illustrative and not in alimiting sense.

We claim:
 1. A method for manufacturing a hardened lead storage batteryelectrode comprising the steps of:preparing an electrolyte by using rawmaterial selected from the group consisting of lead, waste materialcontaining lead, and desulfured lead storage battery electrolyte pasteto form an HBF₄ solution containing lead and lead compounds selectedfrom the group consisting of PbO, Pb(OH)₂ and PbCO₃ ; mixing solids intosaid electrolyte; electrolytically depositing lead onto a plurality ofelectrically conductive surface regions of a cathode in a vesselcontaining said electrolyte mixed with said solids and forming anelectrochemical cell consisting of said cathode, said electrolytesolution and a Cu/Ta/Pt anode by producing a current through saidelectrolyte solution between said cathode and said anode having acurrent density of from approximately 100 to about 2000 A/m² ;maintaining said solids mixed in said electrolyte while electrolyticallydepositing lead and vigorously agitating said electrolyte solution byintroducing air into said vessel through an apertured plate in a bottomof said vessel; and selecting a shape of said electrically conductivesurface regions for producing a selected coupled shape of said leadstorage battery electrode on said electrically conductive surfaceregions simultaneously with the electrolytic lead deposition.
 2. Themethod as defined in claim 1, wherein said electrolyte comprises fromabout 50 to about 300 g Pb⁺⁺ /l, from about 50 to about 200 g free HBF₄/l and from about 1 to about 5 g H₃ PO₄ /l.
 3. The method as defined inclaim 1 wherein the current density is from about 1100 to about 2000A/m².
 4. The method as defined in claim 1 wherein due to a shaping ofthe cathode or an insulating covering of the cathode in a specificpattern, the deposited material at the plurality of electricallyconductive surface regions of the cathode forms a grid-shaped pattern.5. The method as defined in claim 1 further comprising the step ofadding an additive selected from the group consisting of: gelatines,glue, β-naphthol, resorcin, calcium lignin sulfonate and peptone to theelectrolyte in a concentration of from about 0.1 to about 2 g/l.
 6. Themethod as defined in claim 1 further comprising the step of adding apolyacrylic acid amide to the electrolyte as an additional additive in aconcentration from about 0.05 to about 5 g/l.
 7. The method as definedin claim 1 further comprising the step of employing a compound selectedfrom the group consisting of: Y₂ O₃, Al₂ O₃, ZrO₂, SiO₂, TiO₂, SiC, WC,TiC, BaSO₄, BN and Si₃ N₄ in a concentration in the electrolyte fromabout 5 to about 150 g/l each and a metal selected from the groupconsisting of Sn, As, Sb, Bi, Cu, Se, Te and Ag in a concentration inthe electrolyte from about 0.01 to about 5 g/l.
 8. The method as definedin claim 7, wherein the compound selected from the group consisting ofY₂ O₃, Al₂ O₃, ZrO₂, SiO₂, TiO₂, SiC, WC, TiC, BaSO₄, BN and Si₃ N₄ ispresent in a grain size of from about 0.005 to about 5 μm.
 9. The methodas defined in claim 1 further comprising the step of employing a metalselected from the group consisting of Sn, As, Sb, Bi, Cu, Se, Te and Agin a concentration in the electrolyte of from about 0.01 to about 5 g/l.10. The method as defined in claim 1 wherein the electrolytic leaddeposition is implemented at temperatures of from about 30° to about 90°C.
 11. The method as defined in claim 1 further comprising the stepsof:using a cathode composed of a plate of an electrical insulatormaterial with at least one electrically conductive track appliedthereon; wherein the step of electrolytically depositing lead compriseselectrolytically depositing lead on said at least one electricallyconductive track; and arranging said at least one electricallyconductive track such that shaping occurs.
 12. The method as defined inclaim 11, further comprising the steps of:employing a copper track assaid at least one electrically conductive track; manufacturing saidcopper track by depositing a copper layer on the electrical insulatormaterial; covering the copper layer with a phototechnically manufacturedmask and thereby leaving unmasked portions of said copper layer;leaching said unmasked portions of said copper layer phototechnically.13. The method as defined in claim 1 further comprising the step ofafter-coating the electrolytically deposited, hardened lead storagebattery electrode with a pure lead.
 14. A method as defined in claim 1wherein the step of mixing solids into said electrolyte comprisesdissolving said solids into said electrolyte.
 15. A method as defined inclaim 1 wherein the step of mixing solids into said electrolytecomprises suspending finely particulate solids insoluble in lead intosaid electrolyte.
 16. The method as defined in claim 1 wherein saidcurrent vessel has a density of from about 600 to about 2000 A/m².
 17. Amethod for manufacturing a hardened lead storage battery electrodecomprising the step of:preparing an electrolyte by using raw materialselected from the group consisting of lead, waste material containinglead, and desulfured lead storage battery electrolyte paste to form asolution of Fe(BF₄)₂ and Fe(BF₄)₃ and containing lead; mixing solidsinto said electrolyte; electrolytically depositing lead onto a pluralityof electrically conductive surface regions of a cathode in a vesselcontaining said electrolyte mixed with said solids and forming anelectrochemical cell consisting of said cathode, said electrolytesolution and a graphite anode by producing a current through saidelectrolyte solution between said cathode and said anode having acurrent density of from approximately 100 to about 2000 A/m² ;maintaining said solids mixed in said electrolyte while electrolyticallydepositing lead and vigorously agitating said electrolyte solution byintroducing air into said vessel through an apertured plate in a bottomof said vessel; and selecting a shape of said electrically conductivesurface regions for producing a selected coupled shape of said leadstorage battery electrode on said electrically conductive surfaceregions simultaneously with the electrolytic lead deposition.
 18. Themethod as defined in claim 17, wherein said electrolyte comprises fromabout 50 to about 200 g Pb⁺⁺ /l, from about 10 to about 50 g Fe⁺⁺ /l,from about 0.1 to about 5 g Fe⁺⁺⁺ /l and from about 10 to about 100 gfree HBF₄ /l.
 19. The method as defined in claim 17, wherein saidelectrolyte comprises from about 50 to about 300 g Pb⁺⁺ /l, from about50 to about 200 g free HBF₄ /l and from about 1 to about 5 g H₃ PO₄ /l.20. The method as defined in claim 17 wherein the current density isfrom about 1100 to about 2000 A/m².
 21. The method as defined in claim17 wherein due to a shaping of the cathode or an insulating covering ofthe cathode in a specific pattern, the deposited material at theplurality of electrically conductive surface regions of the cathodeforms a grid-shaped pattern.
 22. The method as defined in claim 17further comprising the step of adding an additive selected from thegroup consisting of: gelatines, glue, β-naphthol, resorcin, calciumlignin sulfonate and peptone to the electrolyte in a concentration offrom about 0.1 to about 2 g/l.
 23. The method as defined in claim 17further comprising the step of adding a polyacrylic acid amide to theelectrolyte as an additional additive in a concentration from about 0.05to about 5 g/l.
 24. The method as defined in claim 17 further comprisingthe step of employing a compound selected from the group consisting of:Y₂ O₃, Al₂ O₃, ZrO₂, SiO₂, TiO₂, SiC, SC, TiC, BaSO₄, BN and Si₃ N₄ in aconcentration in the electrolyte from about 5 to about 150 g/l each anda metal selected from the group consisting of Sn, As, Sb, Bi, Cu, Se, Teand Ag in a concentration in the electrolyte from about 0.01 to about 5g/l, the compound and the metal being used as a solid.
 25. The method asdefined in claim 24, wherein the compound selected from the groupconsisting of Y₂ O₃, Al₂ O₃, ZrO₂, SiO₂, TiO₂, SiC WC, TiC, BaSO₄, BNand Si₃ N₄ is present in a grain size of from about 0.005 to about 5 μm.26. The method as defined in claim 17 further comprising the step ofemploying a metal selected from the group consisting of Sn, As, Sb, Bi,Cu, Se, Te and Ag in a concentration in the electrolyte of from about0.01 to about 5 g/l.
 27. The method as defined in claim 17 wherein theelectrolytic lead deposition is implemented at temperatures of fromabout 30° to about 90° C.
 28. The method as defined in claim 17 furthercomprising the steps of:using cathode composed of a plate of anelectrical insulator material with at least one electrically conductivetrack applied thereon; depositing the raw material on said at least oneelectrically conductive track; and arranging said at least oneelectrically conductive track such that shaping occurs.
 29. The methodas defined in claim 28, further comprising the steps of:employing acopper track as said at least one electrically conductive track;manufacturing said copper track by leeching a copper layer that isapplied on the electrical insulator material; and covering the copperlayer with a mask, the mask being manufactured phototechnically.
 30. Themethod as defined in claim 17 further comprising the step ofafter-coating the electrolytically deposited, hardened lead storagebattery electrode a pure lead.
 31. The method as defined in claim 17wherein said current vessel has a density of from about 600 to about2000 A/m².